US20130305962A1 - O/W Wax Dispersions and Gypsum Products Obtainable From These - Google Patents
O/W Wax Dispersions and Gypsum Products Obtainable From These Download PDFInfo
- Publication number
- US20130305962A1 US20130305962A1 US13/644,560 US201213644560A US2013305962A1 US 20130305962 A1 US20130305962 A1 US 20130305962A1 US 201213644560 A US201213644560 A US 201213644560A US 2013305962 A1 US2013305962 A1 US 2013305962A1
- Authority
- US
- United States
- Prior art keywords
- wax
- phase
- gypsum
- gypsum composition
- wax dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 60
- 239000010440 gypsum Substances 0.000 title claims description 114
- 229910052602 gypsum Inorganic materials 0.000 title claims description 114
- 239000000203 mixture Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000001993 wax Substances 0.000 claims description 125
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 239000004203 carnauba wax Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 235000013869 carnauba wax Nutrition 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 238000007127 saponification reaction Methods 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- 239000001175 calcium sulphate Substances 0.000 claims description 5
- 235000011132 calcium sulphate Nutrition 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 235000013871 bee wax Nutrition 0.000 claims description 3
- 239000012166 beeswax Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 4
- 150000002989 phenols Chemical class 0.000 claims 3
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 claims 1
- 239000011505 plaster Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 31
- 239000012188 paraffin wax Substances 0.000 description 16
- 239000011087 paperboard Substances 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000012170 montan wax Substances 0.000 description 13
- 239000005871 repellent Substances 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000010426 asphalt Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003925 fat Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical group O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 244000180278 Copernicia prunifera Species 0.000 description 3
- 235000010919 Copernicia prunifera Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000011507 gypsum plaster Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000025 natural resin Substances 0.000 description 3
- 244000106483 Anogeissus latifolia Species 0.000 description 2
- 235000011514 Anogeissus latifolia Nutrition 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000001922 Gum ghatti Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000019314 gum ghatti Nutrition 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 235000019809 paraffin wax Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 241001133760 Acoelorraphe Species 0.000 description 1
- 240000001889 Brahea edulis Species 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004164 Wax ester Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000003780 insertion Methods 0.000 description 1
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- 229920005610 lignin Polymers 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
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- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/02—Cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2611—Polyalkenes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/34—Natural resins, e.g. rosin
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
- C08L91/08—Mineral waxes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/65—Water proofers or repellants
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1006—Absence of well-defined organic compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
Definitions
- the invention relates to aqueous compounds containing waxes and gypsum products that can be manufactured from these, particularly aerated gypsum and plasterboard.
- Gypsum is calcium sulphate that can be present with and without crystallisation water.
- Naturally occurring gypsum rock is calcium sulphate dihydrate (CaSO 4 ⁇ 2H 2 O); the anhydrous form of calcium sulphate is frequently referred to as anhydrite (CaSO 4 ).
- CaSO 4 calcium sulphate dihydrate
- anhydrite CaSO 4
- “gypsum” refers to naturally occurring gypsum rock, the corresponding products of industrial processes and also the products obtained during the burning of these raw materials.
- Gypsum is ideally suited as a construction and working material, due to the fact that it is easy to dehydrate (dehydration (1)). Dehydration is a reversible process. Exposure to energy drives some or all of the crystallisation water out of the calcium sulphate dihydrate. The reverse reaction after water is added (rehydration (2)) causes the previously burned, i.e. at least partially dehydrated gypsum, to become solid, forming a crystalline structure.
- Naturally occurring gypsum varies in terms of its purity. Natural impurities include, e.g. limestone (e.g. muscovite or dolomite CaCO 3 ⁇ MgCO 3 ), marl, mineral clay (e.g. montmorillonite or caolinite), and occasionally also sand, bitumen or a variety of salts.
- gypsum is also accessible from various technical processes. For example, flue-gas or REA gypsum with a high degree of purity is produced during the desulphurisation of flue gases.
- Gypsum plasterboards are industrially manufactured building boards essentially made up of gypsum, the surfaces and possibly also the longitudinal edges of which are surrounded by firmly adhered paperboard to suit the application.
- the gypsum core surrounded by paperboard may contain air spaces and additives to achieve given properties.
- GKB gypsum plasterboard
- GKBI impregnated gypsum plasterboard
- GKFI fire-resistant gypsum plasterboard
- Gypsum plasterboard is made from gypsum and additives for the gypsum core, as well as high-grade, repeatedly couched paperboard on large belt systems running continuously. Plaster of Paris (low-fired gypsum, produced at temperatures of roughly 120° C. to 180° C.) is frequently used.
- the production process comprises the following steps:
- gypsum wallboards made from gypsum
- gypsum wallboards These are factory-made building panels made from plaster of Paris and water for non-weight-bearing structural components.
- Gypsum wallboards may contain fibres, fillers and additive substances, as well as other additives, and they may be coloured with pigments to distinguish them visually. They have smooth visible surfaces and are designed with alternating tongue and groove finishes on the abutting and storage surfaces.
- water-repellent boards are known.
- Board production takes place in largely automated production plants. Uniform, runny slurry is made from plaster of Paris, water and possibly additives in a dosage and mixing apparatus and used to fill the moulding boxes of the gypsum plasterboard machine. Once the mixture has set, the boards are ejected hydraulically and transported to the dryer. This is followed by drying in heated continuous driers. After drying, the boards are combined into packages or loaded onto pallets.
- Gypsum fibre boards are furthermore referred to as gypsum-based plasterboard.
- gas formers propellants
- the gas formers mainly comprise several material components in which a chemical reaction is activated by the water coupled with the creation of a gas. The resulting gas bubbles force the gypsum slurry up in the mould.
- Foam is mainly produced by atomising water and air enriched with surface-active substances (surfactants).
- aerated gypsum elements produced using the aforementioned method are additionally water-repellent. This involves water-repellent additives being added to the mixer in the mixture preparation phase.
- Gypsum products are provided with additives that delay water absorption, for use in damp areas.
- the impregnating additives are usually added to the gypsum mixture before the gypsum products are made and worked into it uniformly, after which the gypsum mixtures are usually dried in layers at a high temperature of e.g. 100 to 150° C. and then cooled. If the gypsum boards are covered with paperboard, they are referred to as gypsum plasterboards.
- the effect of dampness can cause the paperboard to soften, leading to deformation.
- the use of gypsum plasterboard in damp rooms, such as bathrooms, laundry rooms, etc. is therefore problematic due to its diminishing rigidity and deformation. This has particularly serious effects when the gypsum plasterboard has ceramic tiles adhered to it, for example.
- the dampness causes the paperboard to soften, lose its inner rigidity and split under the weight of the ceramic tiles, causing the layer of paperboard attached to the boards to fall away. The destruction of the remaining gypsum paperboard is then only a matter of time.
- U.S. Pat. No. 3,935,021 describes a gypsum wallboard in which polyvinyl alcohol and a wax-asphalt emulsion are introduced into the gypsum core.
- Wax-asphalt emulsions are widely used in gypsum wallboards, although certain disadvantages are associated with their use.
- an aqueous emulsion is used to make gypsum products water-repellent, which comprises a hydrocarbon wax, a montan wax and an emulsifier/stabiliser system with the addition of polyvinyl alcohol.
- WO 98/09925 describes an aerated gypsum product, which is made water-repellent through the inclusion of an aqueous emulsion, which comprises a hydrocarbon wax, a montan wax and a colloid-stabilised emulsifier system.
- aqueous wax dispersions for making gypsum products water-repellent which contain starch, long-chain alkyl phenols, saponified montan waxes, surfactant, complexing agents and paraffin waxes are known from U.S. Pat. No. 6,585,820.
- U.S. Pat. No. 6,595,553 also mentions surfactant, montan wax and paraffin wax as an integral part of the aqueous wax dispersion.
- the problem addressed by the present invention is that of finding a water-repelling agent that is suitable for both traditional gypsum plasterboard and also for the technically more complex production of aerated gypsum.
- a further problem facing the invention is that of guaranteeing sufficient vapour permeability, despite the water-repellent nature.
- the wax additive must improve the flow performance of the gypsum mixture, bring about a slight change in the reinforcing behaviour of the gypsum, cause a significant improvement in the paperboard adhesion and have a very slight effect on foaming in the process.
- montan waxes a small number of hydrocarbons are contained in montan waxes, but not unsubstantial proportions of montan resins and asphalt substances, whereby the latter contain a not unsubstantial proportion of inorganic ash components (0.4 to 4% by wt.).
- Montan resins and ash components may affect the colour if, for example, a particularly light-coloured gypsum is required when the material is used in visible construction work.
- the hydrocarbon chains in the wax acids and wax alcohols have a chain length of 20 to 34 C units with a maximum of around 30 C units. In this case, the focus lies on chains with a straight-line number of carbon atoms.
- longer-chain alphaolefins hydrated and/or unhydrated
- Fischer-Tropsch waxes can also be used as the basic wax phase.
- natural waxes, fats, fatty alcohols and synthetic and synthetically modified natural resin components are also capable of being used in the composition.
- the O/W wax dispersion according to the invention for use in gypsum products consist of:
- FIG. 1 is a schematic diagram showing the production of O/W emulsions.
- gypsum compositions as described above, containing wax dispersions and the use of wax dispersions in such gypsum compounds or else the gypsum products described above.
- Substances that can be used as aliphatic hydrocarbons according to the invention are paraffin, synthetic Fischer-Tropsch waxes and alphaolefins (AO, hydrated and unhydrated) with a solidification point of over 50° C. and below 95° C. and, particularly, with average C chain lengths greater than 25 in each case.
- Polar compounds within the meaning of the present invention are compounds displaying hydrocarbon chains with per molecule over 18 C atoms and at least one hydroxyl group, an ether group and/or a carboxyl group (—C( ⁇ O)O—), possibly also derivated, i.e. esterified or saponified.
- the polar compounds display no more than three of the aforementioned groups or a total of three polar groups, particularly one or two groups, per molecule overall.
- the further polar compounds may be oxidised and possibly also partially saponified Fisher-Tropsch waxes, oxidised paraffin, oxidised polyethylene, so-called PE wax esters (jointly referred to as oxidised hydrocarbons (HC) or partially saponified oxidised HC's) and modified natural and/or synthetic resins, as well as natural waxes.
- PE wax esters jointly referred to as oxidised hydrocarbons (HC) or partially saponified oxidised HC's
- modified natural and/or synthetic resins as well as natural waxes.
- fats triglycerides
- the acid groups contained in the polar additives may be saponified during the course of the wax dispersion production with the aid of alkaline substances (e.g. potassium or caustic soda).
- the Wax dispersion comprises esterified colophonium resins such as glycerine and/or pentaerythrite maleic acid colophonium resins, beeswax and/or carnauba wax, wherein the colophonium-resins preferably are used in combination, particularly with oxidised HC's and/or partially saponified oxidised HC's.
- esterified colophonium resins such as glycerine and/or pentaerythrite maleic acid colophonium resins, beeswax and/or carnauba wax
- the wax dispersion prefferably contains carnauba wax as a constituent part of the polar compounds, particularly at 1 to 20% by wt., particularly 1 to 15% by wt., relative to the wax phase.
- polar compounds which contain as polar compounds the above oxidised hydrocarbons (HC) or partially saponified, oxidised HC's (greater than 1% by wt.) and carnauba wax (greater than 1% by wt.) or the above oxidised hydrocarbons (HC) or partially saponified, oxidised HC's (greater than 1% by wt.) and the above synthetically modified colophonium resins.
- the water-repellent effect is reinforced if the polar compounds contain as the predominant constituent part oxidised and possibly also partially saponified Fischer-Tropsch waxes, oxidised paraffin, oxidised polyethylene, so-called PE waxes and, as the lesser component, fats (e.g. palm fats or soya oils) and/or fatty alcohols (e.g. Nafol® 20+).
- oxidised paraffin oxidised polyethylene
- PE waxes so-called PE waxes
- fats e.g. palm fats or soya oils
- fatty alcohols e.g. Nafol® 20+
- the wax phase is preferably added to the gypsum slurry in the form of an aqueous wax dispersion, as gypsum board production is water-based and the dosing of the wax phase can therefore be significantly more accurate.
- the preferably small particle size of the disperse wax phase ensures a particularly uniform distribution of the active substance in the gypsum slurry.
- emulsifiers all types used for the production of wax dispersions, i.e. non-ionic, anionic and cationic emulsifier types, but also combinations of these (non-ionic with anionic and non-ionic with cationic) are suitable as emulsifiers.
- Non-ionic and anionic emulsifiers are particularly suitable.
- emulsifiers that achieve stabilisation by concentrating the water phase are also suitable.
- These may be natural resins, for example, (Gum Ghatti, derivated cellulose) or xanthane polymers or else polysaccharide, but also inorganic substances of the bentonite type.
- Particularly suitable as emulsifiers are sulphonates such as naphthaline sulphonate and/or lignin sulphonate, preferably along with a thickening agent such as Gum Ghatti, in particular.
- polyvinyl alcohols may be added to the wax dispersion, particularly up to 0.5 to 4% by wt. relative to the wax dispersion, which are available, for example, as partially hydrolised ethylene vinyl acetate polymers, but also produced from acrylates and other polyvinyl esters. Degrees of hydrolysis of over 70%, particularly over 85%, are desirable, but not a requirement.
- compositions according to the invention are advantageously wax dispersions, which can be produced with the aid of homogenisers.
- at least two phases are combined with one another (pre-emulsion).
- At least the wax-containing phase is heated above the solidification point for this, in order to melt the wax.
- the other phase is the aqueous phase. This is preferably mixed with the emulsifier and is advantageously heated likewise.
- the pre-emulsion is then passed through the circuit e.g. via splitting homogenisers, until the desired particle size of the wax phase is achieved.
- the emulsion is then cooled to temperatures below the solidification point of the wax phase.
- the individual wax particles of the disperse phase are evenly distributed in the aqueous, continuous phase by the process and a wax dispersion with prolonged stability is thereby obtained.
- the wax dispersion is thereby created.
- This is an oil in water (O/W) wax suspension with an average particle diameter of particularly 0.1 to 10 ⁇ m, advantageously 0.5 to 2 ⁇ m.
- the wax dispersion according to the invention is particularly suitable for the production of the water-repellent gypsum compositions described above, particularly those containing or comprising foamed gypsum or aerated gypsum and, in particular, coated gypsum plasterboard, preferably using the aforementioned gypsum.
- FIG. 1 shows how the O/W emulsions are typically produced.
- a wax boiler ( 1 ) fitted with a temperature sensor and temperature monitoring system
- the wax emulsifier ( 2 ), water and hot steam ( 3 ) are produced, agitated and moved into the pre-emulsion boiler ( 4 ) by means of a pump ( 5 ), where the water-emulsifier mixture ( 6 ) is added. Delivery and transfer into the homogeniser ( 8 ) takes place using the pump ( 7 ).
- a cooling medium ( 9 ) the temperature of the emulsion is lowered in the cooling system ( 10 ), e.g. to 30° C., in order to obtain the finished wax dispersion ( 11 ).
- the degree of water repellence can be determined by subjecting the gypsum body to an immersion test. This involves the water absorption being determined in % by wt. after a 120 minute immersion period (H 2 O 120 mins column in the following table). Suitable threshold values in this case are ⁇ 10% by wt. and, particularly, ⁇ 5% by wt. water absorption.
- Table 1 shows the data for the finished wax phases (% stands for % by wt. in each case). It emerges that predominantly hard wax phases (needle penetration at 25° C. ⁇ 20 [0.1 mm] in accordance with ASTM D1321) with solidification points of between 60 and 80° C. and also acid numbers (DIN 51558) of between 0 and 10 (mgKOH/g) and also saponification numbers from 0 to 20 mgKOH/g have a beneficial effect on water repellence. This produces the values required by DIN 18180 of ⁇ 10% by wt. water absorption. The water absorption is therefore significantly reduced compared with the blind value (31%) of the natural gypsum used in this case, which demonstrates the effect of the wax mixtures used as wax dispersions.
- the wax dispersions (WD) were made according to the following suggested formulation:
- the water was heated to approx. 80° C. along with the surfactant and the KOH and agitated for roughly 20 mins.
- the molten (80-100° C.) wax phase was then added and agitated for a further 5 minutes.
- the pre-emulsion was added to the homogeniser and passed through the circuit for 1 minute, after which it was homogenised for 1 minute at a pressure of roughly 200 bar.
- the wax emulsion was then cooled to room temperature during which the wax particles solidified and the wax dispersion was produced.
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Abstract
Description
- This application claims priority to U.S. application Ser. No. 11/989,259 filed on Feb. 12, 2009, which is a U.S. national phase of PCT/DE2006/001293 filed on Jul. 25, 2006, which claims priority to DE 102005035515.3 filed on Jul. 26, 2005, the disclosures of which are incorporated herein by reference for all purposes.
- The invention relates to aqueous compounds containing waxes and gypsum products that can be manufactured from these, particularly aerated gypsum and plasterboard.
- Gypsum is calcium sulphate that can be present with and without crystallisation water. Naturally occurring gypsum rock is calcium sulphate dihydrate (CaSO4×2H2O); the anhydrous form of calcium sulphate is frequently referred to as anhydrite (CaSO4). In the language of this application, “gypsum” refers to naturally occurring gypsum rock, the corresponding products of industrial processes and also the products obtained during the burning of these raw materials.
- Gypsum is ideally suited as a construction and working material, due to the fact that it is easy to dehydrate (dehydration (1)). Dehydration is a reversible process. Exposure to energy drives some or all of the crystallisation water out of the calcium sulphate dihydrate. The reverse reaction after water is added (rehydration (2)) causes the previously burned, i.e. at least partially dehydrated gypsum, to become solid, forming a crystalline structure.
-
(CaSO4×2H2O)+T→(CaSO4×0.5H2O)+1.5H2O -
(CaSO4×2H2O)+T→CaSO4×2H2O -
Gypsum stone+energy→burnt gypsum (1) -
Gypsum stone+energy→burnt gypsum (2) - Naturally occurring gypsum varies in terms of its purity. Natural impurities include, e.g. limestone (e.g. muscovite or dolomite CaCO3×MgCO3), marl, mineral clay (e.g. montmorillonite or caolinite), and occasionally also sand, bitumen or a variety of salts. However, gypsum is also accessible from various technical processes. For example, flue-gas or REA gypsum with a high degree of purity is produced during the desulphurisation of flue gases.
- Gypsum plasterboards are industrially manufactured building boards essentially made up of gypsum, the surfaces and possibly also the longitudinal edges of which are surrounded by firmly adhered paperboard to suit the application. The gypsum core surrounded by paperboard may contain air spaces and additives to achieve given properties.
- Essential mechanical plasterboard properties result from the combined effect of the gypsum core and the paperboard casing. This involves the paperboard acting to reinforce the tension area, which in conjunction with the gypsum core gives the gypsum plasterboard the required strength and flexural rigidity. Various types of gypsum plasterboard (GKB) are distinguished, e.g. those that include additives to delay water absorption (impregnated gypsum plasterboard (GKBI) and impregnated fire-resistant gypsum plasterboard (GKFI)).
- The water absorption and drying-out time of gypsum plaster-board is tested according to DIN 18180 (2 hours' spent in water).
-
GKB/GKF GKBI/GKFI Water absorption in (w/w)% 30-50 <10 Drying-out time in hrs 70 15 - Gypsum plasterboard is made from gypsum and additives for the gypsum core, as well as high-grade, repeatedly couched paperboard on large belt systems running continuously. Plaster of Paris (low-fired gypsum, produced at temperatures of roughly 120° C. to 180° C.) is frequently used. The production process comprises the following steps:
-
- paperboard supplied at the bottom,
- gypsum slurry supplied and distributed by the moulding station while paperboard is simultaneously supplied from above to form the top layer,
- hardening section,
- insertion in a dryer (usually after being divided up into individual boards) and
- delivery and possible trimming of the transverse edges and bundling of the boards.
- In addition, there are also gypsum building materials in the form of wallboards made from gypsum, which are briefly referred to as “gypsum wallboards”. These are factory-made building panels made from plaster of Paris and water for non-weight-bearing structural components. Gypsum wallboards may contain fibres, fillers and additive substances, as well as other additives, and they may be coloured with pigments to distinguish them visually. They have smooth visible surfaces and are designed with alternating tongue and groove finishes on the abutting and storage surfaces. Here, too, water-repellent boards are known.
- Board production takes place in largely automated production plants. Uniform, runny slurry is made from plaster of Paris, water and possibly additives in a dosage and mixing apparatus and used to fill the moulding boxes of the gypsum plasterboard machine. Once the mixture has set, the boards are ejected hydraulically and transported to the dryer. This is followed by drying in heated continuous driers. After drying, the boards are combined into packages or loaded onto pallets.
- Gypsum fibre boards are furthermore referred to as gypsum-based plasterboard.
- The production of gypsum with low bulk densities, particularly so-called foam or aerated gypsum, is the object of many patents and publications. The solutions known hitherto can generally be divided into two groups:
- (1) Use of gas formers (propellants), which are added to the binding agent partially dry or are completely or partially added to the latter only during the aerated gypsum production process via the mixing water. The gas formers mainly comprise several material components in which a chemical reaction is activated by the water coupled with the creation of a gas. The resulting gas bubbles force the gypsum slurry up in the mould.
(2) Undermixing of separately prepared foam, which is added to the mixture in the mixer and immediately causes pores to form in the made-up material slurry. Foam is mainly produced by atomising water and air enriched with surface-active substances (surfactants). - It is also known that aerated gypsum elements produced using the aforementioned method are additionally water-repellent. This involves water-repellent additives being added to the mixer in the mixture preparation phase.
- Gypsum products, particularly gypsum plasterboard, are provided with additives that delay water absorption, for use in damp areas. The impregnating additives are usually added to the gypsum mixture before the gypsum products are made and worked into it uniformly, after which the gypsum mixtures are usually dried in layers at a high temperature of e.g. 100 to 150° C. and then cooled. If the gypsum boards are covered with paperboard, they are referred to as gypsum plasterboards.
- If the gypsum does not receive suitable water-repellent treatment, the effect of dampness can cause the paperboard to soften, leading to deformation. The use of gypsum plasterboard in damp rooms, such as bathrooms, laundry rooms, etc. is therefore problematic due to its diminishing rigidity and deformation. This has particularly serious effects when the gypsum plasterboard has ceramic tiles adhered to it, for example. The dampness causes the paperboard to soften, lose its inner rigidity and split under the weight of the ceramic tiles, causing the layer of paperboard attached to the boards to fall away. The destruction of the remaining gypsum paperboard is then only a matter of time.
- In addition to the diminishing rigidity and deformation, corrosion and mildew can accelerate the destruction. Even the adhesive layer applied to the entire surface for the ceramic tiles, which usually has a synthetic base, cannot inhibit the effect of the dampness.
- The use of silicon or siloxane emulsions/dispersions for impregnation is known. In addition, dispersions based on paraffin or montan waxes are known. However, polymers and resins are also used, which do not fall into the wax category. Polyvinyl alcohols are referred to as polymers. The wax components are in some cases also added to the gypsum mixture in powder form. Mixtures of asphalt or bitumen dispersions, in some cases used in combination with polyvinyl alcohols, in which a silicon compound or a synthetic resin emulsion has been added to the gypsum, are likewise known from the literature.
- However, it is difficult to obtain a satisfactory water-repellent or hydrophobic product, which is sufficiently hydrophobic and, at the same time, facilitates the necessary foam stability to produce an aerated product.
- U.S. Pat. No. 3,935,021 describes a gypsum wallboard in which polyvinyl alcohol and a wax-asphalt emulsion are introduced into the gypsum core. Wax-asphalt emulsions are widely used in gypsum wallboards, although certain disadvantages are associated with their use.
- In U.S. Pat. No. 5,437,722 an aqueous emulsion is used to make gypsum products water-repellent, which comprises a hydrocarbon wax, a montan wax and an emulsifier/stabiliser system with the addition of polyvinyl alcohol.
- WO 98/09925 describes an aerated gypsum product, which is made water-repellent through the inclusion of an aqueous emulsion, which comprises a hydrocarbon wax, a montan wax and a colloid-stabilised emulsifier system.
- Other aqueous wax dispersions for making gypsum products water-repellent, which contain starch, long-chain alkyl phenols, saponified montan waxes, surfactant, complexing agents and paraffin waxes are known from U.S. Pat. No. 6,585,820. U.S. Pat. No. 6,595,553 also mentions surfactant, montan wax and paraffin wax as an integral part of the aqueous wax dispersion.
- The problem addressed by the present invention is that of finding a water-repelling agent that is suitable for both traditional gypsum plasterboard and also for the technically more complex production of aerated gypsum. A further problem facing the invention is that of guaranteeing sufficient vapour permeability, despite the water-repellent nature. Furthermore, the wax additive must improve the flow performance of the gypsum mixture, bring about a slight change in the reinforcing behaviour of the gypsum, cause a significant improvement in the paperboard adhesion and have a very slight effect on foaming in the process.
- The effectiveness of wax dispersions in gypsum products is crucially dependent on the composition. It is obviously important for the internal surface of the micropores to be sealed in the gypsum. On the other hand, the pores must not be completely closed off, in order to retain the desired vapour permeability. This cannot be achieved with pure hydrocarbon dispersions according to our findings. In the past, montan wax was used here in the mixture with paraffin. Montan wax is a hard fossil wax of vegetable origin, which has survived the carbonisation process virtually unchanged. It therefore occurs in some brown coal as an extractable element. Important chemical parameters include the acid number (AN) and saponification number (SN) of the montan wax. Furthermore, a small number of hydrocarbons are contained in montan waxes, but not unsubstantial proportions of montan resins and asphalt substances, whereby the latter contain a not unsubstantial proportion of inorganic ash components (0.4 to 4% by wt.).
- Montan resins and ash components may affect the colour if, for example, a particularly light-coloured gypsum is required when the material is used in visible construction work. The hydrocarbon chains in the wax acids and wax alcohols have a chain length of 20 to 34 C units with a maximum of around 30 C units. In this case, the focus lies on chains with a straight-line number of carbon atoms.
- When using wax dispersions in impregnated gypsum plasterboard (GKBI) and impregnated fire-resistant gypsum plasterboard (GKFI), it is generally of particular significance that these do not have a negative effect on the paperboard's adhesion to the surface of the gypsum core. Furthermore, the emulsifier systems must also be based on optimum adhesion of the paperboard layer and minimum interference with the foaming behaviour of the gypsum slurry. Surprisingly, it was found that the water-repelling effect in gypsum products known hitherto predominantly from wax dispersions containing montan wax can also be achieved with other specially selected polar synthetic and natural components. Apart from paraffin and in claim 1 obligatory named polar long-chain compounds, longer-chain alphaolefins (hydrated and/or unhydrated) and Fischer-Tropsch waxes can also be used as the basic wax phase. Also capable of being used in the composition are natural waxes, fats, fatty alcohols and synthetic and synthetically modified natural resin components.
- It emerged that the desired water-repellence could also be achieved with the help of wax phases without montan wax. In this case, other wax phases and also other polar additives were identified as useable. This produces lighter/whiter gypsum products that can also be used for visible construction, as the wax phases, particularly the additives used, display significantly lower ash contents or none at all and also contain no dark asphalt and resin components.
- The O/W wax dispersion according to the invention for use in gypsum products consist of:
- at least 30% by wt., particularly 30 to 80% by wt., preferably around 40 to 65% by wt., water,
- at least 20% by wt., particularly 70 to 20% by wt., preferably 35 to 60% by wt, wax phase as the disperse phase, wherein the wax phase or the total substances used to create the wax phase (i.e. before further saponification, where appropriate, through optional alkalisation or the alkali/earth alkali addition) display a saponification number greater than 0.2 mgKOH/g,
- at least 0.1% by wt., particularly 0.5 to 5% by wt., of an emulsifier or thickening agent as the dispersal agent, and
- maximum 20% by wt., particularly under 10% by wt., other substances, particularly as a component of the continuous phase,
wherein the wax phase consists of the following, each based on the wax phase:
- (a) 50 to 98% by wt. aliphatic hydrocarbons (HC) or mixtures thereof, each with a solidification point above 50° C. and below 95° C., particularly 55 to 80° C.,
- (b) 2 to below 50% by wt., particularly 5 to 20% by wt., from polar, long-chain compounds with chain lengths of at least 18 carbon atoms, particularly aliphatic, containing
- at least one carboxyl group, possibly partially or fully derivated,
- an ether group and/or
- at least one hydroxyl group (—OH)
- per molecule, but no more than three of the afore-mentioned groups together, particularly polar, long-chain compounds, which contain per molecule at least one carboxyl group, possibly partially or fully derivated, alongside possibly up to two other groups per molecule, including the carboxyl group, possibly derivated,
and possibly - (c) maximum 10% by wt., particularly below 5 and preferably below 0.5% by wt., other substances solid at room temperature, particularly aromatic-free, or none and
- (d) maximum 3% by wt. substances liquid at room temperature (at room temperature and normal pressure), particularly below 1.5% by wt.,
wherein the wax phase comprises at least carnauba wax, esterified colophonium-resins and/or beeswax and wherein the wax dispersion has a pH value higher than 11. -
FIG. 1 is a schematic diagram showing the production of O/W emulsions. - Advantageous embodiments are the subject of the dependent claims or are described below. Also claimed are gypsum compositions, as described above, containing wax dispersions and the use of wax dispersions in such gypsum compounds or else the gypsum products described above.
- Substances that can be used as aliphatic hydrocarbons according to the invention are paraffin, synthetic Fischer-Tropsch waxes and alphaolefins (AO, hydrated and unhydrated) with a solidification point of over 50° C. and below 95° C. and, particularly, with average C chain lengths greater than 25 in each case.
- Polar compounds within the meaning of the present invention are compounds displaying hydrocarbon chains with per molecule over 18 C atoms and at least one hydroxyl group, an ether group and/or a carboxyl group (—C(═O)O—), possibly also derivated, i.e. esterified or saponified. The polar compounds display no more than three of the aforementioned groups or a total of three polar groups, particularly one or two groups, per molecule overall.
- The further polar compounds may be oxidised and possibly also partially saponified Fisher-Tropsch waxes, oxidised paraffin, oxidised polyethylene, so-called PE wax esters (jointly referred to as oxidised hydrocarbons (HC) or partially saponified oxidised HC's) and modified natural and/or synthetic resins, as well as natural waxes. Furthermore, fats (triglycerides), e.g. of vegetable origin, such as palm, soya and rapeseed fats, are suitable. The acid groups contained in the polar additives may be saponified during the course of the wax dispersion production with the aid of alkaline substances (e.g. potassium or caustic soda). These lyes are overdosed in this case, so that pH values of over 11 are obtained. This also has a favourable effect on the resistance of the wax dispersions to biological decomposition and mildew. The Wax dispersion comprises esterified colophonium resins such as glycerine and/or pentaerythrite maleic acid colophonium resins, beeswax and/or carnauba wax, wherein the colophonium-resins preferably are used in combination, particularly with oxidised HC's and/or partially saponified oxidised HC's.
- It is particularly preferable for the wax dispersion to contain carnauba wax as a constituent part of the polar compounds, particularly at 1 to 20% by wt., particularly 1 to 15% by wt., relative to the wax phase.
- Particularly advantageous are mixtures of polar compounds, which contain as polar compounds the above oxidised hydrocarbons (HC) or partially saponified, oxidised HC's (greater than 1% by wt.) and carnauba wax (greater than 1% by wt.) or the above oxidised hydrocarbons (HC) or partially saponified, oxidised HC's (greater than 1% by wt.) and the above synthetically modified colophonium resins. The percentages by weight each relate to the wax phase (=100% by wt.).
- The water-repellent effect is reinforced if the polar compounds contain as the predominant constituent part oxidised and possibly also partially saponified Fischer-Tropsch waxes, oxidised paraffin, oxidised polyethylene, so-called PE waxes and, as the lesser component, fats (e.g. palm fats or soya oils) and/or fatty alcohols (e.g. Nafol® 20+). This produces synergistic effects. In other words, the reduction in water absorption when additives are combined increases even more than can be expected from the sum of the individual effects.
- In this case, the wax phase is preferably added to the gypsum slurry in the form of an aqueous wax dispersion, as gypsum board production is water-based and the dosing of the wax phase can therefore be significantly more accurate. Furthermore, the preferably small particle size of the disperse wax phase (average particle size less than 2 μm and particularly roughly 1 μm) ensures a particularly uniform distribution of the active substance in the gypsum slurry.
- In principle, all types used for the production of wax dispersions, i.e. non-ionic, anionic and cationic emulsifier types, but also combinations of these (non-ionic with anionic and non-ionic with cationic) are suitable as emulsifiers. Non-ionic and anionic emulsifiers are particularly suitable. Furthermore, emulsifiers that achieve stabilisation by concentrating the water phase are also suitable. These may be natural resins, for example, (Gum Ghatti, derivated cellulose) or xanthane polymers or else polysaccharide, but also inorganic substances of the bentonite type. Particularly suitable as emulsifiers are sulphonates such as naphthaline sulphonate and/or lignin sulphonate, preferably along with a thickening agent such as Gum Ghatti, in particular.
- Furthermore, polyvinyl alcohols may be added to the wax dispersion, particularly up to 0.5 to 4% by wt. relative to the wax dispersion, which are available, for example, as partially hydrolised ethylene vinyl acetate polymers, but also produced from acrylates and other polyvinyl esters. Degrees of hydrolysis of over 70%, particularly over 85%, are desirable, but not a requirement.
- The compositions according to the invention are advantageously wax dispersions, which can be produced with the aid of homogenisers. In this case, at least two phases are combined with one another (pre-emulsion).
- At least the wax-containing phase is heated above the solidification point for this, in order to melt the wax. The other phase is the aqueous phase. This is preferably mixed with the emulsifier and is advantageously heated likewise.
- The pre-emulsion is then passed through the circuit e.g. via splitting homogenisers, until the desired particle size of the wax phase is achieved. The emulsion is then cooled to temperatures below the solidification point of the wax phase. The individual wax particles of the disperse phase are evenly distributed in the aqueous, continuous phase by the process and a wax dispersion with prolonged stability is thereby obtained. The wax dispersion is thereby created. This is an oil in water (O/W) wax suspension with an average particle diameter of particularly 0.1 to 10 μm, advantageously 0.5 to 2 μm. The wax dispersion according to the invention is particularly suitable for the production of the water-repellent gypsum compositions described above, particularly those containing or comprising foamed gypsum or aerated gypsum and, in particular, coated gypsum plasterboard, preferably using the aforementioned gypsum.
-
FIG. 1 shows how the O/W emulsions are typically produced. In a wax boiler (1) fitted with a temperature sensor and temperature monitoring system, the wax emulsifier (2), water and hot steam (3) are produced, agitated and moved into the pre-emulsion boiler (4) by means of a pump (5), where the water-emulsifier mixture (6) is added. Delivery and transfer into the homogeniser (8) takes place using the pump (7). By means of a cooling medium (9), the temperature of the emulsion is lowered in the cooling system (10), e.g. to 30° C., in order to obtain the finished wax dispersion (11). - The degree of water repellence can be determined by subjecting the gypsum body to an immersion test. This involves the water absorption being determined in % by wt. after a 120 minute immersion period (H2O 120 mins column in the following table). Suitable threshold values in this case are <10% by wt. and, particularly, <5% by wt. water absorption.
- Table 1 shows the data for the finished wax phases (% stands for % by wt. in each case). It emerges that predominantly hard wax phases (needle penetration at 25° C.<20 [0.1 mm] in accordance with ASTM D1321) with solidification points of between 60 and 80° C. and also acid numbers (DIN 51558) of between 0 and 10 (mgKOH/g) and also saponification numbers from 0 to 20 mgKOH/g have a beneficial effect on water repellence. This produces the values required by DIN 18180 of <10% by wt. water absorption. The water absorption is therefore significantly reduced compared with the blind value (31%) of the natural gypsum used in this case, which demonstrates the effect of the wax mixtures used as wax dispersions. The wax dispersions (WD) were made according to the following suggested formulation:
- 60% by wt. water; 3% by wt. Marlophen® NP 10 (non-ionic surfactant from Sasol Olefins and Surfactants GmbH on an ethoxylate base); 1% by wt. KOH (45% by wt.) and 36% wax phase.
- Laboratory production of the wax dispersion:
- The water was heated to approx. 80° C. along with the surfactant and the KOH and agitated for roughly 20 mins. The molten (80-100° C.) wax phase was then added and agitated for a further 5 minutes. The pre-emulsion was added to the homogeniser and passed through the circuit for 1 minute, after which it was homogenised for 1 minute at a pressure of roughly 200 bar. The wax emulsion was then cooled to room temperature during which the wax particles solidified and the wax dispersion was produced.
-
TABLE 2 Substances used Name Type Manufacturer Paraffin Sasolwax 6403 (Fully Paraffin) Sasol Wax GmbH EP 64/66 Carnauba wax Natural palm wax Kahl & Co Resin Escorez 1102 F, aliphatic Exxon Mobil hydrocarbon resin -
TABLE 1 Properties of different wax dispersions Paper Start of End of Flow Data adhe- harden- harden- mea- Composition EP PenN25 (1) AN (2) SN (3) Foam H2O sion (6) ing (6) ing (6) sure (6) No. Dispersion/unit (° C.) (0.1 mm) (mgKOH/g) reduction (4) 120 min (5) (% by wt.) Min (*) * Gypsum blind value 31 = 6 9 = VI * Montan wax/paraffin 70.5 10 3 8.7 = 2.4 + +2 +4 Higher ** V2 ** Montan wax/paraffin 64.5 11 3.1 9 = 2.5 + +2 +4 Higher 1 Carnauba wax/ 66 16 0.3 1.4 = 2.3 + = +4 Higher paraffin (2.5% carnauba) 2 Carnauba wax/ 65 11 0.5 4.1 Smaller 4.6 + +2 +2 = paraffin (5% carnauba) 3 Carnauba wax/ 67 11 1 8.2 = 3.6 + = +4 Thicker resin/paraffin (10% carnauba, 5% escorez) 4 Carnauba wax/ 66 19 1 8.2 — 6 — — — — paraffin (10% carnauba wax) Key to Table 1 (*) Blind value of the untreated natural gypsum 31% ** These two dispersions serve for comparison purposes with the state of the art (1) Solidification point ASTM D 938 (2) Needle penetration ASTM D 1321 at 25° C. (3) Acid number according to DIN 51558 (4) Saponification number according to DIN 51559 (5) Water absorption according to DIN 81180 (6) Internal house methods + better than blind value (possibly better than gypsum value by how much) = equal to blind value — not measured
Claims (21)
Priority Applications (2)
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US13/644,560 US8741056B2 (en) | 2005-07-26 | 2012-10-04 | O/W wax dispersions and gypsum products obtainable from these |
US14/274,274 US9981874B2 (en) | 2005-07-26 | 2014-05-09 | O/W wax dispersions and gypsum products obtainable from these |
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DE102005035515A DE102005035515A1 (en) | 2005-07-26 | 2005-07-26 | O / W wax dispersions and gypsum products available therefrom |
US11/989,259 US20090194004A1 (en) | 2005-07-26 | 2006-07-25 | O/W wax dispersions and plaster products obtainable from them |
PCT/DE2006/001293 WO2007012316A1 (en) | 2005-07-26 | 2006-07-25 | O/w wax dispersions and plaster products obtainable from them |
US13/644,560 US8741056B2 (en) | 2005-07-26 | 2012-10-04 | O/W wax dispersions and gypsum products obtainable from these |
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PCT/DE2006/001293 Continuation WO2007012316A1 (en) | 2005-07-26 | 2006-07-25 | O/w wax dispersions and plaster products obtainable from them |
US12/989,259 Continuation US8411881B2 (en) | 2008-04-22 | 2009-04-21 | Electret capacitor microphone with one-piece vocal cavity component |
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US13/644,560 Expired - Fee Related US8741056B2 (en) | 2005-07-26 | 2012-10-04 | O/W wax dispersions and gypsum products obtainable from these |
US14/274,274 Expired - Fee Related US9981874B2 (en) | 2005-07-26 | 2014-05-09 | O/W wax dispersions and gypsum products obtainable from these |
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EP (1) | EP1907480B1 (en) |
AT (1) | ATE442419T1 (en) |
AU (1) | AU2006274324B2 (en) |
CA (1) | CA2614395C (en) |
DE (2) | DE102005035515A1 (en) |
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US10113094B2 (en) | 2014-10-30 | 2018-10-30 | Henry Company, Llc | Phase-change materials from wax-based colloidal dispersions and their process of making |
US10913826B2 (en) | 2014-09-26 | 2021-02-09 | Henry Company, Llc | Powders from wax-based colloidal dispersions and their process of making |
US20210147686A1 (en) * | 2018-05-25 | 2021-05-20 | SasoI Wax GmbH | Wax Composition Comprising Linear Hydrocarbons, Branched Hydrocarbons and Oxidized Hydrocarbons, Aqueous Dispersion Thereof, Method to Produce Such Wax Composition and Dispersion and Use Thereof as Carnauba Wax Replacement |
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- 2006-07-25 DE DE502006004808T patent/DE502006004808D1/en active Active
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- 2006-07-25 AT AT06775748T patent/ATE442419T1/en active
- 2006-07-25 AU AU2006274324A patent/AU2006274324B2/en not_active Ceased
- 2006-07-25 PL PL06775748T patent/PL1907480T3/en unknown
- 2006-07-25 CA CA2614395A patent/CA2614395C/en not_active Expired - Fee Related
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US10113094B2 (en) | 2014-10-30 | 2018-10-30 | Henry Company, Llc | Phase-change materials from wax-based colloidal dispersions and their process of making |
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DE502006004808D1 (en) | 2009-10-22 |
ZA200800034B (en) | 2009-03-25 |
US20090194004A1 (en) | 2009-08-06 |
EP1907480A1 (en) | 2008-04-09 |
PL1907480T3 (en) | 2010-04-30 |
CA2614395A1 (en) | 2007-02-01 |
EP1907480B1 (en) | 2009-09-09 |
DK1907480T3 (en) | 2010-01-04 |
CA2614395C (en) | 2011-05-31 |
WO2007012316A1 (en) | 2007-02-01 |
AU2006274324A1 (en) | 2007-02-01 |
US8741056B2 (en) | 2014-06-03 |
US9981874B2 (en) | 2018-05-29 |
ATE442419T1 (en) | 2009-09-15 |
US20140245928A1 (en) | 2014-09-04 |
DE102005035515A1 (en) | 2007-02-01 |
AU2006274324B2 (en) | 2012-01-19 |
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